This invention relates to a membrane electrode assembly (MEA) for use in an electrochemical cell, such as a hydrogen fuel cell, which comprises an annealed polymer electrolyte membrane (PEM) and may additionally comprise an annealed catalyst layer.
Briefly, the present invention provides a membrane electrode assembly (MEA) comprising an annealed polymer electrolyte membrane (PEM). The polymer electrolyte is cast, coated or otherwise formed from a suspension and subsequently annealed to a temperature of 120xc2x0 C. or greater or more preferably 130xc2x0 C. or greater.
In another aspect, the present invention provides an MEA having one or more annealed catalyst layers, which are annealed to a surface of the annealed PEM.
It is an advantage of the present invention to provide an MEA having superior performance in a hydrogen fuel cell, including superior mechanical strength and durability.
The present invention provides a membrane electrode assembly (MEA) comprising an annealed polymer electrolyte membrane (PEM) and optionally one or more annealed catalyst layers.
The polymer electrolytes useful in the present invention are preferably acid-functional fluoropolymers or salts thereof, such as Nafion(copyright) (DuPont Chemicals, Wilmington Del.) and Flemion(trademark) (Asahi Glass Co. Ltd., Tokyo, Japan). The polymer electrolytes useful in the present invention are preferably copolymers of tetrafluoroethylene and one or more fluorinated, acid-functional comonomers. Preferably the polymer electrolyte bears sulfonate functional groups. Most preferably the polymer electrolyte is Nafion. The polymer electrolyte preferably has an acid equivalent weight of 1200 or less, more preferably 1100 or less, more preferably 1050 or less, and most preferably about 1000. The polymer electrolyte is preferably obtained as an aqueous dispersion. The dispersion may also include organic solvents including alcohols. More preferably the dispersion includes a mixture of water and alcohols. Such dispersions are sometimes referred to as solutions. Preferably the dispersion excludes solvents having a boiling point above 100xc2x0 C., i.e., greater than that of water.
The polymer electrolyte is first cast, coated or otherwise formed from a suspension into a suitable shape, preferably a thin layer, and subsequently annealed. Any suitable method of coating or casting may be used, including bar coating, spray coating, slit coating, brush coating, and the like.
The annealing temperature is preferably greater than 120xc2x0 C. and more preferably 130xc2x0 C. or more. The time of annealing is preferably sufficient to allow the surface of the polymer electrolyte to reach a suitable annealing temperature and more preferably sufficient to allow the entire mass of the polymer electrolyte to reach a suitable annealing temperature. In thin layers, times of less than a minute may be sufficient. In the annealed material, polymer particles which are distinct in the dispersion and which remain distinct in the cast or coated membrane coalesce to form a continuous solid phase with reduced or preferably obliterated boundaries.
A polymer electrolyte membrane (PEM) according to the present invention preferably has a thickness of less than 50 xcexcm, more preferably less than 40 xcexcm, more preferably less than 30 xcexcm, and most preferably about 25 xcexcm. Preferably the PEM contains no supporting structural material or matrix in addition to the polymer electrolyte, and more preferably the PEM is composed only of annealed polymer electrolyte.
The PEM according to the present invention may be sandwiched between two catalyst coated gas diffusion layers (CCGDL""s) to form a membrane electrode assembly (MEA). The CCGDL may be formed by coating a gas diffusion layer (GDL) with a catalyst ink. The catalyst ink preferably comprises additional polymer electrolyte material which is annealed during bonding to the previously annealed PEM. The annealing temperature is preferably greater than 120xc2x0 C. and more preferably 130xc2x0 C. or more.
In one preferred method, a catalyst dispersion or ink is first made by dispersing carbon-supported catalyst particles in a dispersion of a polymer electrolyte. The carbon-supported catalyst particles are preferably 50-60% carbon and 40-50% catalyst metal by weight, the catalyst metal preferably comprising Pt for the cathode and Pt and Ru in a weight ratio of 2:1 for the anode. The electrolyte dispersion is preferably an aqueous dispersion, preferably of a solid polymer electrolyte such as Nafion(trademark) (DuPont Chemicals, Wilmington Del.). The polymer electrolyte preferably has an equivalent weight of 1200 or less, more preferably 1100 or less, more preferably 1050 or less, and most preferably about 1000. The mixture is preferably heated with high shear stirring for 30 minutes and diluted to a coatable consistency.
The gas diffusion layer is electrically conductive and permeable to fluids and preferably comprises carbon, such as carbon fibers. The gas diffusion layer is preferably Toray Carbon Paper (Toray Industries, Inc., Tokyo, Japan). Prior to coating with the catalyst dispersion, the gas diffusion layer has preferably been coated with a hydrophobic layer such as Teflon(trademark), preferably by dipping in an aqueous suspension thereof, and then has preferably been coated with a carbon black dispersion. The carbon black dispersion is preferably an aqueous dispersion comprising carbon black and Teflon and optionally a surfactant such as TRITON X-100 (Union Carbide Corp., Danbury, Conn.). More preferably, the dispersant is a combination of water and isopropyl alcohol, preferably comprising more than 60% by weight isopropyl alcohol. The carbon black dispersion is preferably coated onto the dried Toray paper at a wet thickness of 0.01 to 0.1 mm. The Teflon and carbon black coated GDL is preferably dried in an oven at 380xc2x0 C. for 10 minutes. This coated GDL is then further coated with the catalyst dispersion prepared above, preferably in an amount yielding 0.2-5 mg of catalyst metal (Pt or Pt plus Ru) per square centimeter, preferably about 0.5 mg of catalyst metal (Pt or Pt plus Ru) per square centimeter, to form a catalyst-coated gas diffusion layer (CCGDL).
The PEM according to the present invention is sandwiched between two catalyst coated gas diffusion layers (CCGDL""s), with the catalyst coating facing the PEM. Preferably, the MEA is pressed, most preferably to a fixed fraction of its original thickness. Prior to pressing, a gasket of Teflon-coated glass fiber is placed on each side. The CCGDL""s are smaller in surface area than the PEM, and each fits in the window of the respective gasket. The height of the gasket is 70% of the height of the CCGDL, to allow 30% compression of the CCGDL when the entire assembly is pressed. Preferably the degree of compression is between 0% and 60%, more preferably 10%-50%, more preferably 20%-40%, and most preferably about 30% as indicated. The pressing temperature is preferably 120xc2x0 C. or greater or more preferably 130xc2x0 C. or greater, such that the ink is annealed to the previously annealed PEM during pressing.
Alternately, the catalyst ink may be applied to both sides of the PEM and the catalyst-coated PEM sandwiched between two GDL""s.
Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.